1,2-dihydro-8-carbamoyloxyquinolines

ABSTRACT

Heterocyclic compounds of the formula   WHEREIN R1 is hydrogen, C1-C4 alkyl, C3-C5 alkenyl or C3-C5 alkinyl, R2 is hydrogen, C1-C4 alkyl or optionally substituted C1-C6 acyl, R3 is hydrogen, C1-C6 alkyl optionally substituted by C1-C4 alkoxy groups or cyano, C3-C5 alkenyl or C3-C5 alkinyl, R4 and R5 are each hydrogen or C1-C4 alkyl, R6 and R7 are each hydrogen or C1-C4 alkyl or together are a further bond between the C atoms to which they are attached in the heterocyclic ring, and R8 is hydrogen, C1-C4 alkyl or halogen, The compound being in the form of the free base or of an acid addition salt thereof, processes for their manufacture and use as agents for pest control.

ilniteti ttes Niitles June 18, 1974 1,2-D1HYDRO-8-CARBAMOYLOXYQUINOLINES [75] inventor: Erwin Nikles, Liestal, Switzerland[73] Assignee: Ciba-Geigy AG, Basel, Switzerland [22] Filed: Sept. 7,1971 [21] Appl. No.: 178,427

[30] Foreign Application Priority Data Sept. 10, 1970 Switzerland13491/70 Aug. 4, 1971 Switzerland 11467/71 [52] U.S. Cl 260/283 CN,71/94, 260/283 P, 260/283 SY, 260/286 R, 260/287 R, 260/287 OX, 424/258[51] int. Cl C0711 33/40 [58] Field of Search 260/287 R, 283 CN [56]References Cited UNITED STATES PATENTS 2,566,723 9/1951 Gardner 260/287R 3,088,916 5/1963 Roman 260/289 R 3,149,117 9/1964 Brown 260/287 R3,362,960 l/1968 Hodel 260/287 R 3,384,538 5/1968 Hodel 260/287 R3,538,099 11/1970 Rohr 260/287 R 3,539,578 11/1970 Brown 260/287 R Rr in ary Examiner-Donald G. Dads Attorney, Agent, or Firm-Harry Falber;Frederick H. Rabin 5 7 ABSTRACT Heterocyclic compounds of the formulaflit Rz-N-C 0-0 3 wherein R is hydrogen, Ci-C alkyl, C -C alkenyl or C Calkinyl,

R ishydrogen, C C alkyl or optionally substituted C -C acyl,

R is hydrogen, C C alkyl optionally substituted by C -C alkoxy groups orcyano, C -C alkenyl or C -C alkinyl,

R and R are each hydrogen or C C alkyl,

R,; and R are each hydrogen or C -C alkyl or together are a further bondbetween the C atoms to which they are attached in the heterocyclic ring,and

R is hydrogen, C -C alkyl or halogen, v

The compound being in the form of the free base or of an acid additionsalt thereof, processes for their manufacture and use as agents for pestcontrol.

13 Claims, No Drawings l ,2-DIHYDRO-8-CARBAMOYLOXYQUINOLINES wherein Ris hydrogen, C,C alkyl, C -C alkenyl or C -C alkinyl,

R is hydrogen, C -C alkyl or optionally substituted C C acyl,

R is hydrogen, C,C alkyl optionally substituted by C,C alkoxy groups orcyano, C -C alkenyl or C C alkinyl,

R,; and R are each hydrogen or C -C alkyl,

R and R are each hydrogen or C -C alkyl or together are a further bondbetween the C atoms to which they are attached in the heterocyclic ring,and

R is hydrogen, C -C alkyl or halogen,

the compound being in the form of the free base or of an acid additionsalt thereof.

The term halogen includes fluorine, chlorine, bromine and iodine.

Preferred among the compounds of the invention are those in which:

R is hydrogen, methyl, ethyl, n-propyl, isopropyl, allyl, crotyl,methallyl, propargyl, Z-butinyl, 3-butin- 2-yl,1,1-dimethyl-2-propin-l-yl,

R is hydrogen, methyl, ethyl, n-propyl, isopropyl, or is optionallychloro or bromo substituted acetyl, propionyl, butyryl, capryl orisomers thereof,

R is hydrogen, optionally methoxy, ethoxy or CN- substituted methyl,ethyl, n-propyl, isopropyl, nbutyl, isobutyl, or sec. butyl, or isallyl, methallyl, crotyl, propargyl, 2-butinyl, 3-butin-2-yl or 1, l-dimethyl-2-propinl -yl,

R and R are each hydrogen, methyl, ethyl or npropyl, or one of the twoof them can be isopropyl,

R and R are hydrogen, methyl, ethyl or a further bond between the twocarbon atoms to which they are joined in the heterocyclic ring, and

R is hydrogen, methyl, ethyl, chlorine or bromine, these compounds beingin the form of free bases or acid addition salts.

Both inorganic and organic acids can form salts with the free amine ofFormula I. Both neutral salts and acid salts may be formed.

Suitable inorganic acids are hydrochloric acid, hydrobromic acid,sulphuric acid, phosphoric acid, arsenic acid, hydriodic acid, nitricacid, perchloric acid and others.

Suitable organic acids are, for example, low aliphatic optionallyhalo-substituted monoand dicarboxylic acids such as acetic acid,monodiand trichloroacetic acid, propionic acid, a-chloropropionic acid,maleic acid, pivalic acid, benzene sulphonic acid, p-toluenesulphonicacid, naphthaline sulphonic acid, methane sulphonic acid, sulphamic acidand others.

In certain cases, the stability of the carbamate is increased by theformation of acid addition salts.

The compounds of Formula I have strong biocidal action against insects,arachnids and worm pests such as nematodes. The effectiveness extendsabove all to pest types of the orders Saltatoria (Teltigonidae,Gryllidae, Gryllotalpidae), Blattaria, Heteroptera (Reduviidae,Phyrrh0c0riae,. Cimidae), Homoptera (Cicacina, Aphidina, Pseudococcidae,Coc'cina), Hymenoptera, C0- leoptera (Scarabaeidae, Dermestidae,Coccinellidae, Tenebrionidae, Chrysomelidae, Bruchidae), Lepidoplera(Tineidae, Noctuidae, Lymantriidae, Pyralidae), Diptera v(Culicidae,Tipulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae), Aphanipterq(Pulicidae) as well as of the order Acarina (Ixodidae, Argasidae,Tetranychidae, Dermanyssia'ae).

Generally, the compounds are effective against all development stagessuch as eggs, larvae, nymphs or pupae and adults or imagos.

Plant pathogenic bacteria and fungi can also be combated with thecompounds of Formula I, even those which attack the plants from the soiland cause trachaeomycoses. Inter alia, these are representatives of thegenus:

Alternaria Aphanomyces Botrytis Cercosporella Fusarium HelminthosporiumOlpidium Ophiobolus Phoma Phytophthora Pythium Rhizoctonia SclerotiniaSclerotium Thielavia Thielaviopsis Verticillium Among the nematodes,there should be mentioned, for example: Aphelenchus ritzemabosi,Aphelenchus fragariae, Aphelenchus oryzae, Ditylenchus dipsaci,Meloidogyne arenaria, Meloidogyne incognita, Heterodera rostochiensi,Heterodera schachtii or Paratylenchus, Xiphinema and Rhadopholus.

The compounds of Formula I work partly in a chemosterilizing way againstinsects.

Thereby, plant-influencing properties are observed, which can change themorphology of the plant or its development cycle, or they can evenbeeffective as herbicides.

Molluscs, especially snails which are schistosome transfer agents, arekilled by compounds of Formula I.

The principal area of use of the compounds noted is, however, thecombating of insects, acarina and nematodes.

The compounds of Formula I can be used, for example, against aphids suchas the peach-potato aphid (Myzus persicae) and the black bean aphid(Doralis fabae); scale insects such as Aspidiotus hederae, Lecaniumhesperidium, Pseudococcus maritimus; Thysanoptera, such asHercinothripsfemoralis, and bugs such as the beet bug (Piesma quadrara)or the bed bug (Cimex lectularus); moth and butterfly grubs such asPlutella maculipermis, Lymanrria dispar; and particularly beetles suchas the grain weevil (Sitophilus granarius Colorado beetle (Leplino tarsadecemlineata) Mexican bean weevil (Epilachna varivestis); and typesliving in the soil such as wire worms (Agriotes sp.) or white grubs(Melolontha melolontha); Orthoptera such as the German cockroach(Blattella germam'ca); and the house cricket (Acheta domesticus);termites, such as Reiiculitermes; Hymenoptera, such as ants; Lepidopterasuch as Chilo suppressalis; Diptera, such as the fruit fly (Drosophilamelanogaster), the Mediterranean fruit fly (Ceratiris capitata), thehouse fly (Musca domestica) as well as midges and mosquitoes, e.g.(Aedes aegypti and Anopheles stephensi).

Compounds of Formula I are particularly effective in combatingrepresentatives of the order Acarina, such as, for example Eulaelaps,Echinolaelaps, Laelaps, Haemogamasus, Dermanyssus, Ornithonyssus,Allodermanyssus, particularly Allodermanyssus sanguineus, Pneumonyssus,Amblyomma, Aponomma, Boophilus, Dermacentor, Haemophysalis, Hyalomma,Ixodes, Margaropus, Rhipicephalus, Ornithodorus; Otobius, Cheyletidae,e.g. Cheyletus, Psorergates, Demodicidae, Trombiculidae, e.g. Tromicula,Eutrombicula, Schongaslia, Acomatacw rus, Neoschongastia, Euschongastia,Sarcopliformes e.g. Notoedres, Sarcoptes, Knemidokoptes, Psoroptidae,e.g. Psoroptes, Chorioptes, Otodecres and Tetranychidae e.g. Tetmnychustelarius; Tetranychus urticae.

.A particularly important group of compounds included in Formula I arethose of the formula wherein R is hydrogen or methyl, R' is hydrogen,methyl, methoxymethyl, ethoxymethyl, cyanomethyl, B-cyanoethyl, ethyl ormethoxyethyl, R, is hydrogen or methyl, R is hydrogen, methyl or ethyl,and R' and R are either both hydrogen or are a further bond betweentheir respective C-atoms of the heterocyclic ring, together with theiracid addition salts.

As suitable individual compounds for pest control, the following shouldbe noted: l,2-dihydro-2,2-dimethyl-8-quinolyl-N- methylcarbamate,1,2-dimethyl-l ,2,3 ,4-tetrahydro-8-quinolyl-N- methylcarbamate,

Z-methyl-l ,2,3,4-tetrahydro-8-quinolyl-N- methylcarbamate, 3-methyll,2,3 ,4-tetrahydro-8-quinolyl-N- methylcarbamate, 4-methyll,2,3,4-tetrahydro-8-quinolyl-N- methylcarbamate,

1,2-dimethyll 2.3.4-tetrahydro-8-quinolyl-N- methylcarbamate, 3,4-dimethyll 2.3,4-tetrahydro-8-quinolyl-N- methylcarbamate.

5 S-methyl-l,2,3,4-tetrahydro-8-quinolyl-N- methylcarbamate, l,Z-dihydro-l1,2,-dimethyl-8-quinolyl-N- methylcarbamate, 1,2 ,3,4-tetrahydro-S-quinolyl-N-methylcarbamate,

1O l-allyl-2.2-dimethyl-l ,2-dihydro-8-quinolyl-N- methylcarbamate,2,2dirneth vl-1,Z-dihydro-l(Z-propinyl)-8-quinolyl-N- methylcarbamate,

l ,2-dihydro-2,2dimethyl-8-quinolyl-N,N-dimethylcarl5 bamate,

methylcarbamate,

l ,2,3 ,4-tetrahydro-2,2,5-dimethyl-8-quinolyl-N- methylcarbamate,

l,Z-dihydro-Z,S-dimethyl-Z-ethyl-El-quinolyl-N- methylcarbamate,

S-chlor-l ,Z-dihydro-Z,2-dimethyl-8-quinolyl-N- methylcarbamate,l-ethyll ,2,3,4-tetrahydro-8-quinolyl-N- methylcarbamatc,

l-allyl-l ,2,3,4-tetrahydro-8-quinolyl-N- methylcarbamate, l-allyl-l,2,3 ,4-tetrahydro-8-quinolyl-N-acetyl-N- methylcarbamate 1(2-propinyl l,2,3 ,4-tetrahydro-S-quinolyl-N- methylcarbamate, l-cyanmethyl-l,2,3,4-tetrahydro-S-quinolyl-N- methylcarbamate,

V l-cyanethyl-l ,2,3,4-tetrahydro-S-quinolyl-N- 33 methylcarbarnate,

l-(Z-methoxyethyl )-l 2,3,4-tetrahydro-8-quinolyl-N- methylcarbamate,

l-( 3-chlorallyl)- l ,2,3 ,4-tetrahydro-8-quinolyl-N- methylcarbamate vl-(2-chlorallyl)- l ,2,3,4tetrahydro-8-quinolyl-N- methylcarbarnate,Z-methyl- 1 -n-propyl-l 2,3,4-tetrahydro-8-quinolylN- methylcarbamate,l-n-butyl-Z-methyll ,2,3 ,4-tetrahydro-S-quinolyLN- methylcarbamate,

l-allyl-2-methyll ,2,3,4-tetrahydro-8-quinolyl-N- methylcarbamate,2-methyll -(2-propinyl )-l ,2,3,4-tetrahydro-8-quinolyl- 5GN-methylcarbamate,

l ,2,3 .4-tetrahydro-8-quinolyl-N,N-dimethylcarbamate,

Z-methyl-l .2,3,4-tetrahydro8-quinolyl-N,N-dimethylcarbarnate,

S 5 6-methyl l ,2,3,4-tetrahydro-8-quinolyl-N- methylcarbamate,l,Z-dihydro-Z,2dimethyl-8-quinolylN-acetyl-N- methylcarbamatc,1,2-dimethyll ,2,3,4-tetrahydro8-quinolyl-N-acctyl- N-methylcarbamate,l-methyl-l ,2,3.4-tetrahydro-8-quinolyl-N-acetyl-N- methylcarbarnate,l,2-dihydro-2,2-dimethyl l -ethyl-8-quinolyl-N- methylcarbamate,2-methyll-n-propyll ,2,3 ,4-tetrahydro-8 N,N-dimethylcarbamate.

The invention also relates to compounds of the formula -quinolyl- 6 solong as R";, is not H. If, on the other hand, R";, is H, then thereactions given for Formulae II, III and IV no longer proceed clearly inthe observed direction, on account of the reactivity of the free amine.In these cases it is expedient to react the aromatic 8-oxyquinolinederivative of the formula wherein R" is hydrogen, alkyl, C C alk en ylor l C -C alkinyl, R" is hydrogen, C -C alkyl or optionallyhalosubstituted C -C acyl, R" is hydrogen, optionally C 'C alkoxy orcyano-substituted C -C alkyl, or is C C alkenyl or C C alkinyl, R" andare hydrogen or C C alkyl, R and R are hydrogen or C C alkyl or togetherwith their respective carbon atoms form a bond, and R" is hydrogen, C -Calkyl or halogen, the acid addition salts of these compounds being alsoincluded.

Worthy of particular mention are those compounds of Formula la in whichR",, R",, and R" are each hydrogen or methyl, R is methyl or acetyl, Ris hydrogen, ethyl, propyl and isopropyl, n-butyl, sec. butyl,cyanomethyl, allyl, 2-chloroallyl, 3-chloroallyl or propargyl, R",, andR" are each hydrogen or together are a further carbon-carbon bond, andR" is hydrogen, methyl or chlorine.

The carbamates of Formula Ia can be prepared by known methods.

For example, a phenol of the formula wherein R" is not H and R" to R"have the mean ings given for Formula I, can be reacted with an aliphaticisocyanate corresponding to R, or an aliphatic carbamic acid chloridecorresponding to R and/or Rllz.

The carbamates of Formula I can also be obtained by reaction of achlorocarbonate of the formula with a corresponding amine of the formulacorresponding to Formula II or its chlorocarbonate corresponding toFormula III or its bis-[ 8-oxyquinolyl] carbonate corresponding toFormula IV to give the carbamate, and then partially hydrogenating inthe presence of Pd/C to the l,2-dihydro or l,2,3,4-tetrahydroderivative. In a few cases, an R;; substituent can also be introduced byquaternizing the ring nitrogen atom and then partially hydrogenating inthe l,2,-position or the l,2,3,4-position in the presence of Pd/C.

The substituent R" can be introduced inter alia with e.g. lithiumorganic compounds LiR l,2-dihydro-8-oxyquinolyl carbamates can beobtained suitably by cyclizing an O-alkinyl aminophenyl carbamate in thepresence of Cu and/or cuprous salts, e.g. CuCl. Insofar as R";, is notH, then starting from the corresponding O-alkinyl aminophenol of theformula HA R"g (VII) this can be cyclized in the presence of Cu and/orcuprous salts and, as described above, converted into the desiredcarbamate.

l,2,3,4-tetrahydro-8-oxyquinolyl carbamates can also be obtainedaccording to choice by subsequent hydration in the presence of Pd/C from8- oxyquinolylcarbamates or from 1,2-dihydro-8- oxyquinolylcarbamates.

The compounds of Formula I can be used as pest control agents with atleast one of the following additives: extenders, suspending agents,emulsifying agents, thickening agents, adhesives, wetting agents and orfertilizers, as well as optionally further pesticides or baits.Extenders are solid or liquid diluents. Among pesticides are includedparticularly insecticides, acaricides, nematocides, bactericides andfungicides.

Pest control agents, usually containing 0.1 to 95 percent by weight,preferably 1 to percent by weight, of the new compounds of Formula I cantake various forms, in dry or damp liquid or solid condition. Shapedcarrier materials such as flycards or fly papers, paper strips orgranulates can be impregnated with the active substances. By means ofsprays a gaseous phase of the active material can be generated.

They can also be used in almost pure form without additives by usingsuitably finely dividing spraying apis spraying from aircraft.

For the manufacture of directly sprayable solutions of compounds ofFormula I, for example, mineral oil fractions of high to average boilingrange may be used, such as diesel oil or kerosene, coal tar oil and oilsof vegetable or animal origin, also hydrocarbons such as alkylatednaphthalines and tetrahydronaphthalene, optionally with the use ofxylene mixtures, cyclohexanols, ketones and furthermore chlorinatedhydrocarbons such as trichlorethane, trichlorethylene or tri andtetrachlorobenzenes. Advantageously, organic solvents boiling at over100C are used.

Aqueous application forms are particularly suitable prepared fromemulsion concentrates, pastes or wettable powders by the addition ofwater. As emulsifying or dispersing agents there can be used non-ionicmaterials e.g. condensation products of aliphatic alcohols, amines orcarboxylic acids having a long chain hydrocarbon group of about 10 to 20carbon atoms with ethylene oxide, such as the condensation product ofoctadecyl alcohol and 25-30 mol ethylene oxide, that of technicaloleylamine and mol ethylene oxide, or that of dodecylmercaptan and 12mol ethylene oxide. Among anionic emulsifiers which can be used, mentionshould be made of the sodium salt of dodecyl alcohol sulphuric acidester, the sodium salt of dodecylbenzene sulphonic acid, the potassiumor triethanolamine salt of oleic acid or abietic acid or mixtures ofthese acids, or the sodium salt of a petroleum sulphonic acid. Ascationic dispersing agents there are quaternary ammonium compounds suchas cetylpyridinium bromide or dioxyethyl dodecyl ammonium chloride.

For manufacturing dusting and spreading agents, talcum, kaolin,bentonite, calcium carbonate, calcium phosphate and even coal, corkflour, wood flour and other materials of vegetable origin can be used.The various use forms can be provided in known fashion with additivematerials which improve distribution, adherence, rain resistance orpenetration. These are, for example, fatty acids, resins, glues, caseinsor alginates.

Dusts with a content of 5-10 percent by weight of active substance canbe made by diluting such a wettable powder with a finely divided solidcarrier. Wetting and dispersing agents may also be left out or replacedby others.

For combating ground insects, termites or rice pests in paddy fields,the use of granulates has proved to be very effective.

Such granulates can be very easily manufactured by dissolving an activesubstance according to Formula I in an organic solvent and applying theso obtained solution to a granulated material such as attapulgite, SiOlime, bentonite etc. and then evaporating the organic solvent again.

Polymer granulates may also be used. They can be manufactured by mixingthe active substance of Formula I with polymerizable compounds(urea/formaldehyde, dicyandiamide/formaldehyde, melamine/formaldehyde orothers) whereafter careful polymerization is carried out which does notaffect the active substance, and wherein during the gel-formation stage,granulation is carried out. It is more favourable to take ready-madeporous polymer granules (urea/formaldehyde polyacrylonitrile, polyesteror others) with a given surface and a favourable predeterminedabsorption/- desorption ratio, to impregnate this with the activesubstance, eg in the form of a solution (in a lowboiling solvent) and toremove the solvent.

Such polymer granules can be used in the form of microgranulates of bulkdensity preferably of 300 to 600 g per litre, also with the aid ofdusting apparatus. Dusting can also take place over extended crop fieldswith the aid of aircraft.

Naturally further pesticides, fertilizers. surface active agents ormaterials for increasing the specific gravity such as BaSO, can be addedto the granulates,

Granulates can also be obtained by compacting the carrier material withactive substance and additives and then disintegrating the compact.

The action of the phosphorus compound, according to the invention, canbe increased by synergists. Suitable for this are, for example, sesamex.piperonyl cyclonene, piperonyl butoxide, piperonal bis {2-(butoxyethoxy) ethyl} acetate, sulphoxide. propyl isome, N-(2-ethylhexyl)-5-norbornen-2.3- dicarboxamide, octachlordipropylether.2-nitrophenylpropargylether, 4-chlor2-nitrophenylpropargylether,2,4,5-trichlorphenyl-propargylether.

As examples for broadening the spectrum of activity of the compounds ofthe invention, the following insecticides, nematocides or acaricides arenoted: Bis-0,0-diethylphosphoric acid anhydride (TEPP) Dimethy](2,2.2-trichlorl -hydroxyethyl) phosphonate (TRICHLORFON)l,2-dibrom-2,2-dichlorethyldimethylphosphate LED)2,Q-dichlorvinyldimethylphosphate (DICHLORVOS) Z-methoxycarbamyll-rnethylvinyldimethylphosphate (MEVINPHOS) Dimethyllmethyl-2-(rnethylcarbamoyll phate cis (MONOCROTOPHOS)3-(dimethoxyphosphinyloxy)-N,N-dimethyl-ciscrotonamide (DICROTOPHOS2-chlorO-Z-diethylcarbamoyll -methylvinyldimethylphosphate(PHOSPHAMIDON) 0,0-diethyl-0(or S)-2(ethylthio)-ethylthiophosphate(DEMETON) S-ethylthioethyl-0,0-dimethyl-dithiophosphate OMETON)0,0-diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE)0,0-diethyl-S-Z-ethylthio)ethyldithiophosphate SULFOTON)0,0-dimethyl-S-2-(ethylsulphinyl)ethylthiophosphate (OXYDEMETONMETHYL)0,0-dimethyl-S-( l,Z-dicarbethoxyethyldithiophosphate (MALATHION)0,0,0,0-tetraethyl-S,S-methylene-bis-dithiophosphate (ETHION)O-ethyl-S,S-dipropyldithiophosphate 0,0-dimethyl-S(N-methyl-N-formylcarbamoylmethyll-dithiophosphate MOTHION) 0,0-dimethyl-S-(N-methylcarbamoylmethyl )dithiophosphate (DIMETHOATE) vinylphos- (THL(FOR

0,0-dimethyl-0-p-nitrophenylthiophosphate (PA RATHION-METHYL) 0,0-diethyl-0-p-nitrophenylthiophosphate (PARA- THION)O-ethyl-O'p-nitrophenylphenylthiophosphate (EPN) 0,0-dimethyl-0-(4-nitro-m-tolyl )thiophosphate (PENI- TROTHION) l iDiethyl-S-Z-(ethylsulphinyl )ethyl (OXYDISULFOTON)Bis-0,0-diethylthiophosphoric acid anhydride (SUL- FOTEP) Dimethyl-l,3-di(carbomethoxy)- l -propen-2-ylphosphate Dimethyl-( 2 ,2,2-trichlorl-butyroyloxyethyl )phosphate (BUTONATE) 0,0-dimethyl-O-(2,2-dichlorl-methoxyvinyl )phosphate Bis-(dimethylamido)fluorphosphate(DIMEFOX) 3 ,4-dichlorobenzyl-triphenylphosphoniurnchloride.Dimethyl-N-rnethxymethylcarbamoylmethyldithiophosphate (FORM OCARB AM)0,0-diethyl-O-( 2,2-dichlorl -chlorethoxyvinyl )phosphate0,0-dirnethyl-0( 2,2-dichlorl -chlorethoxyvinyl )phos phateO-ethyl-S,S-diphenyldithiolphosphateO-ethyl-S-benzyl-phenyldithiophosphonate0,0-diethyl-S-benzyl-thiolphosphate 0,0-dimethyl-S-(4-chlorphenylthiomethyl )dithiophosphate (METHYLCARBOPHENOTHION)0,0-dimethyl-S-(ethylthiomethyl)dithiophosphateDiisopropylaminofluorphosphate (MIPAFOX) O ,O-dimethyl-S-(morpholinylcarbarnoylme thyl )dithiophosphate (MORPHOTH ION)Bismethylamido-phenylphosphate 0,0-dimethyl-S-(benzenesulphonyl)dithiophosphate 0,0-dimethyl-(S and O)-ethylsulphinylethyithiophosphate 0,0-diethyl-0-4-nitrophenylphosphateTrie thoxy-isopropoxy-bis( thiophosphinyl )disulphide 2-methoxy-4 l-l-l,3 ,2,be nzodioxaphosphorin-2-oxide Okta,ethylpyrophosphoramide(SCHRADAN) Bis (dimethoxythiophosphinylsulphido phenylmethane N,N,N ,N-tetramethyldiamidofluorphosphate (DIME- FOX)O-phenyl-O-p-nitrophenyl-rnethanthiophosphonate (C- OLEP) O-methyl-O-(2-chlor-4-tert. butyl-phenyl )-l lmethylamidothiophosphate (NARLENE)O-ethyl-O-2( 2,4-dichlorphe nyl )-phe nylthiophosphonate0,0diethyl-O(4methylmercapto-3,5 dimethylphenyl )-thiophosphate 4,4'-bis-( 0,0-dimethylthiophosphoryloxy diphenyldisulphide0,0-di(B-chlorethyl )-O-(3-chlor-4-methyl-cumarinyl- 7 )phosphate S-( l-phthalimidoethyl )-0,0-diethyldithiophosphate 0,0dime thyl -O-(3-chlor-4-diethylsulphamylphenyl thiophosphate O-me thyl-0-(2-carbisopropoxyphenyl )-arnidothiophosphate-(0,0-dimethylphosphoryl)-6-chlor-bicyclo( 3 2.0 heptadiene( 1,5)O-methyl-0-(Z-i-propoxycarbonyl-1-methylvinyl)ethylamidothlophosphate.

The following examples will serve to illustrate the invention.

dithiophosphate EXAMPLE 1 O-aminophenyl N-methylcarbamate A solution of196 parts O-nitrophenyl-N-acetyl carbamate in 700 volumes of glacialacetic acid and in the presence of 2.4 parts l0 percent palladium carbonwas shaken in a hydrogen atmosphere. After ending the hydrogen takeup,the catalyst was filtered off and the filtrate evaporated in vacuo. Theresidue was mixed up with water. filtered, dried and crystallized fromchloroform. M.Pt. l26l28C.

The following can be manufactured similarly:

Oamino-4-tolyl N-methylcarbamate, MPt. l l2] 15- CC,

2-arnino-4-chlorphenyl N-rnethylcarbamate. MPt. l29-l33C. from4-chlor2-nitro-phenyl N-methylcarbamate, M.Pt. lO6llOC,

O-aminophenyl N.N-dimethylcarbarnate. MPt. 6364C. from O-nitrophenylN,N-dimethylcarbamate (MPL 5657C). O-( l l-dimethyl-2-propinylamino)phenyl-N- methylcarbamate 83 partsO-aminophenylNmethylcarbamate were suspended in 300 parts water in anitrogen atmosphere. Then 5 parts of cuprous chloride and 62 parts3-chloro-3-methyl-l-butine were added dropwise with stirring. Bycontinuous addition of 5 percent caustic soda the mixture was kept at pH4-5 and by cooling at about 20C.

After the addition of the 3-chloro-3-methyl-lbutine was ended, themixture was stirred for a further /2 hour at 20C, and then treated with300 volume parts of ether, brought to a pH of 7 with sodium bicarbonatesolution and filtered through Celtite. The organic phase was separated,washed with water, dried over anhydrous sodium sulphate and evaporatedto dryness.

After recrystallization, the O-( l ,l-dimethyl-Z- propinylarninolphenylN-methyl carbamate was obtained with a melting point of 8992C.

Analogously there can be made:

O,( l, l -dimethyl-2-propinyl-amino)4-tolyl carbamate,

2-( l l -dirnethyl-Z-propinyl-amino) 4-chlorphenyl N- butylcarbamatelVLPt. -1 l4C,

O-( lethyl-l -methyl-2-propinyl-arnino )4-tolyl methylcarbamate,

O-( 1,l-dimethyl-Z-propinyhaminc)phenyl N,Ndimethylcarbamate, MPt.66-68C.

l ,Z-dihydro-Z,Z-dimethyLS-quinolyl-N- methylcarbamate. Active substanceNo. l

30 parts phenyl-N-methylcarbamate were dissolved in volume parts etherand treated with 60 parts water, l5 parts copper powder, and 1.5 partscuprous chloride. The mixture was boiled under reflux in a nitrogenatmosphere for about 70 hours, well stirred, and finally filteredthrough Celtite. The ethereal phase was separated. dried over anhydroussodium sulphate and evaporated. The residue was chromatographed onsilica gel. The material eluted with methylene chloride was crystallizedfrom cyclohexane. Mit. l00iO3C.

EXAMPLE 2 2,2-dimethyl-l ,2,3,4-tetrahydro-8-quinolylN- methylcarbamate.Active substance No. 2

30 parts, l,Z-dihydro-Z,2-dimethyl-S-quinolyl-N- methylcarbamate weredissolved in 300 volume parts of dry dioxanev The solution was shaken inthe presence of l. .5 parts 5 percent palladium carbon at 2030 C in ahydrogen atmosphere. After takeup of 3430 vol- N-methyb O-{ l,1-dimethyl-2-propinyl-amino) ume parts (normal conditions) of hydrogen,the hydrogenation rate dropped sharply. The solution was then filteredand evaporated. The residue was recrystallized once from alcohol/water.M.Pt. 111-1 16C.

EXAMPLE 3 1,2-dihydro-2,2-dimethyl- 1 2-propinyl)-8-quinolyl N-methylcarbamate. Active substance No. 3

A mixture of 70 parts l,2-dihydro-2,2-dimethyl-8- quinolylN-methylcarbamate, 20 parts potassium iodide, 65 parts 2,6-lutidine and150 volume parts dimethylformamide were warmed to 60C in a nitrogenatmosphere, and treated with stirring with 108 parts propargyl bromideadded in portions. The mix was stirred for 14 hours at 60C, then cooledand treated with 500 volume parts ether and 200 parts water. The organicphase was separated, washed with 100 parts water, dried over anhydroussodium sulphate, filtered and evaporated The residue was crystallizedfrom benzene-cyclohexane. M.Pt. 108-112C.

EXAMPLE 4 1 ,2, 3 ,4-tetrahydro-8-quinaldy1-N-methylcarbamate. Activesubstance No. 4

216 parts S-quinaldyl-N-methylcarbamate were dissolved in 600 parts byvolume glacial acetic acid and treated with parts 10 percent palladiumcarbon. The mixture was shaken in a hydrogen atmosphere, until theamount of hydrogen required for the saturation of two double bonds hadbeen taken up. The catalyst was filtered off and the filtrate evaporatedin vacuo. The residue was dissolved in ether and washed with ice-coldcaustic soda. The ethereal solution was evaporated and the residuechromatographed on silica gel. The material eluted with toluene andmethylene chloride was crystallized from cyclohexane. 1V1.Pt. 77-82C.

EXAMPLE 5 1 ,2,3 ,4-tetrahydro-8-quinolyl-N-methylcarbamate. Activesubstance No. 5

'Analogously to the way described in Example 2,8-quinolyl-N-methylcarbamate was hydrogenated. The crude product waswashed with soda solution and crystallized from toluene. M.Pt. 112-117C.

EXAMPLE 6 l-cyanomethyl- 1 ,2,3 ,4-tetrahydro-8-quinolyl-N-methylcarbamate. Active substance No, 6

To a solution of 52 parts 1,2,3,4-tetrahydro-8-quinolyl-N-methylcarbamate in 100 parts by volume dimethyl formamide and33 parts 2,6-lutidine, at room temperature, there was added dropwise 51parts iodoacetonitrile. The mixture was then kept at 50C for 14 hours.The solution was diluted with 300 volume. parts ether, washed thricewith water, dried and evaporated. The residue was crystallized fromtoluene. M.Pt. 1 13-1 18C.

EXAMPLE7 l-allyl-S-hydroxy- 1 ,2,3 ,4-tetrahydroquinoline A mixture of97 parts 8-hydroxy-l,2,3,4-

tetrahydroquinoline, 300 volume parts dimethyl formamide, 80 partspyridine and 48 parts potassium iodide was treated at 40 with stirringwith 83 parts allyl chloride added dropwise, and kept at 90C for a fewhours. The mix was evaporated in vacuo. The residue was treated with 500parts each of ether and water. The organic phase was evaporated awaywith water and washed with 2N soda solution, and evaporated. Thecrystalline residue was mixed up with ether and filtered. The crudeproduct melted at 6977C. l-allyl- 1 ,2,3,4-tetrahydro-S-quinolyl-N-acetyl-N- methylcarbamate Active substanceNo. 7

12 parts crude l-allyl-8-hydroxy-1,2,3,4- tetrahydroquinoline weredissolved in 40 parts toluene and treated with 19.5 parts aqueous 40percent trimethylaminesolution. Into the solution, cooled to 0C, therewas added dropwise with stirring 17.8 parts N-acetyl-N-methyl-carbamicacid chloride. The mix ture was then kept for 14 hours at roomtemperature.

The organic phase was-separated, washed with parts water and 50 parts2N-caustic soda, dried over anhydrous sodium sulphate, filtered andevaporated. As residue, oily l-allyl-l,2,3,4-tetrahydro-8-quinolylN-acetyl-N-methylcarbamate was obtained.

EXAMPLE 8 8-hydroxy- 1 2-propinyl 1 ,2,3,4-tetrahydro-quinoline partspropargyl chloride were added dropwise at 60C with stirring to a stirredmixture of 97 parts 8 hydroxy-l,2,3,4-tetrahydroquinoline, 86 parts 2,6-lutidine, 35 parts potassium iodide and 300 parts by volume dimethylformamide. The temperature of the mix was then held at 40C for 2 hours.The mixture was cooled and treated with 500 parts by volume ether and500 parts water. The organic phase was dried, washed with water andevaporated. The residue was diluted with methanol, precipitated withwater and dried. 1-(2-propinyl)-1,2,3,4-tetrahydro-8-quinolyl-N-methylcarbamate. Active substance No. 8

54 parts crude S-hydroxy-l-(2-propinyl)-1,2,3,4- tetrahydro quinolineand 0.2 parts triethylene diamine were dissolved in 200 parts by volumedioxane, and treated with 30 parts methyl isocyanate in portions,whereon the temperature rose to 40C. The solution was kept at 40C for 14hours and then evaporated. The residue was chromatographed on silicagel. The product eluted with methylene chloride was crystallized fromtoluenehexane. M.Pt. 103-105C.

EXAMPLE 9 8-hydroxy- 1 ,2-dimethyl- 1 ,2,3 ,4-tetrahydro-quinoline In anitrogen atmosphere at C a stirred mixture of 147 parts S-hydroxy-l,2,3,4-tetrahydroxyquinoline, 64 parts calcined sodium carbonate and 350volume parts dimethyl formamide were treated with 151 parts dimethylsulphate added dropwise. The mixture was then stirred for 14 hours at Cand then evaporated in vacuo. The residue was treated with 300 volumeparts ether and 300 parts water. The ethereal phase was separated,washed twice with 200 parts water and several times with 10 percentcaustic soda. The caustic soda extracts were purified and neutralizedwith concentrated hydrochloric acid. The product was extracted withether and distilled under high vacuum. B.Pt. 76-80C/0.035 mml-lg.

In similar fashion, 8-hydroxy-l ,2,3,4-tetrahydroquinaldine can bealkylated with the aid of the corresponding alkyl, alkenyl or alkinylbromide or chloride with nitrogen. These intermediate products canbe-used further without purification.

l ,Z-dimethyl-1,2,3,4-tetrahydro-8-quinolyl-N- methylcarbamate. Activesubstance No. 9

68 parts 8-hydroxy-1,2-dimethyl-l,2,3 ,4- tetrahydroquinoline weredissolved in 200 parts by volume hexane, and treated with 0.2 partstriethylenediamine and with 36 parts methyl isocyanate added inportions, whereon an exothermic reaction took place. The mixture waskept at 40C for 14 hours and then evaporated. The oily product was driedunder high vac uum at 45C.

EXAMPLE l 8-hydroxy-2-methyl- 1 -n-propyl-1 ,2,3,4- tetrahydroquinolineAnalogously to the method described in Example 7,8-hydroxy-1,2,3,4-tetrahyclroquinoline was converted into 8-hydroxy2-methyl- 1 -n -propyl-1 ,2 ,3 ,4- tetrahydroquinoline with n-propylbromide. M.Pt. 102- -103C/0.16 mmHg. 2-methyl- 1 -n-propyl- 1 ,2, 3,4-tetrahydro-8-quinolyl N,N-dimethylcarbamate. Active substance No. 10

40 parts 8-hydroxy-2-methyl- 1 -n-propyll ,2,3 ,4- tetrahydroquinolinewere dissolved in 100 parts by volume hexane, and treated with 31.8parts 40 percent aqueous trimethylamine solution and dropwise with 23.1parts dimethyl carbamic acid chloride. The temperature of the mixturewas kept at 30C for several hours, and the organic phase then separatedoff and evaporated in vacuo. Oily Z-methyl-l-n-propyl-1,2,3 ,4-tetrahydro-S-quinolyl N,N-dim ethylcarbamate was obtained as residue.

in fashion similar to Examples 1-10 the following compounds weremanufactured: Active substance No.

183-methy1- l ,2,3 ,4-tetrahydro-8-quinoly1-N- methylcarbamate. 12

1 84-methyl-1,2,3,4-tetrahydro-8-quinolyl-N- methylcarbamate. 13

1 83 ,4-dimethyl-1,2,3 ,4-tetrahydro-8-quinolyl methylcarbamate. 14

1 85-methyl- 1,2,3 ,4-tetrahydro-8-quinolyl-N- methylcarbarnate. 15

18 1 ,2,2-trimethyl.-1 ,2-dihydro-8-quinolyl-N- methylcarbamate. 16

1 8 1 -a1lyl-2,2-dimethy1-1 ,2-dihydro-8-quinolyl-N- methylcarbamate.M.Pt. 72-76C. 17

182,2-dimethyl-1,2-dihydro-8-quinolyl-N,N-dimethylcarbamate. M.Pt. 74C.18

182,2,5-trimethyl-l ,2-dihydro-8-quinolyl-N- methylcarbamate. M.Pt.97103C. 19

182,2,5-trimethyl-1 ,2,3 ,4-tetrahydro-8-quinolyl-N- methylcarbamate.M.Pt. 133-138C. 20

182,5-dimethyl-2-ethyl-1 ,2-dihydro-8-quinolyl-N- methylcarbamate. M.Pt.87-90C. 21

1 85-ch1or-1 ,2-dihydro-2,Z-dimethyl-8-quinolyl-N- methylcarbamate 94C.

l8l-ethyl-1,2.3,4tetrahydro-S-quinolyl-N- methylcarbamate. 23

l81-allyl-1,2,3,4-tetrahydro8-quinolyl-N- methylcarbamate. M.Pt. 68-72C.

181-cyanethyll,2,3,4-tetrahydro-8-quinolyl-N- methylcarbamate.

181-(2-methoxyethyl)-l,2,3,4-tetrahydro-8- quinolyl-N-methylcarbamate.

181-(3-chlorallyl)-1,2,3,4-tetrahydro-8-quinolyl- N-methylcarbamate.M.Pt. '74-78C.

18 l-( 2-chloral1yl)- l ,2,3 ,4-tetrahydro-8-quinolyl-N-methylcarbamate. M.Pt. C.

1 82-methyll -n-propyl' l ,2,3,4-tetrahydro-8-quinolyl-N-methylcarbamate. M.Pt. 96-98C 1 8 l -n-butyl-2-methyl- 1 ,2,3 ,4tetrahydro-8- quinolyl-N-methylcarbamate. M.Pt. 5861C 181-allyl-2-methy1-1,2,3 ,4-tetrahydro-8-quinolyl- N- methylcarbamate(oil).

182-methyl-1-(2-propinyl)-1,2,3,4-tetrahydro-8-quinolyl-N-methylcarbamate. M.Pt. 90-92C.

1 81,2,3,4-tetrahydro-8-quinolyl-N,N-dimethylcarbamate.

182-methyl- 1 ,2,3,4-tetrahydro-S-quinolyl-N,N- dimethylcarbamate.

1 86-methyll ,2,3 ,4-tetrahydro-8-quinolyl-N- methylcarbamate.

182,2-dimethyll ,2-dihydro-8-quinolyl-N-acetyl N-methylcarbamate.

18l-methyl-1,2,3,4-tetrahydro-8-quinolyl-N- acetyl-N-methylcarbamate.

1 82,2-dimethyl-l-ethyl-1,2-dihydro8-quinolyl-N- methylcarbarnate.

18 l -methylcyanato-1 ,2-dihydro-2,2-dimethyl-8-quinolyl-N-methylcarbamate.

1 81-methylcyanato-l ,2-dihydro-2,Z-dimethyl-S-quinolyl-N,N-dimethylcarbamate.

1 81-(2-chlorallyl)-1,2,3,4-tetrahydro-8-quinolyl-N,N-dimethylcarbamate.

1 81-(2-ch1orallyl)-1,2,3,4-tetrahydro-8quinolyl-N-acetyl-N-methylcarbamate.

l 81-propyl-1,2,3,4-tetrahydro-S-quinolyl-N- methylcarbamate.

1 8 1 -isopropyl- 1 ,2,3 ,4-tetrahydro-S-quinolyl-N- methylcarbamate.

l 8 l -isopropyl-l ,2,3,4-tetrahydro-8-quinolyl-N- methylcarbamate.

45 l-sec. butyl-l ,2,3,4-tetrahydro-8-quinolyl-N- methylcarbamate.

181-ethyl-2-methyl-1,2,3,4-tetrahydro-8-quinolyl- N-methylcarbamate.

47 l-( n) butyl-2-methyl-l ,2,3 ,4-tetrahydro-N,N-

dimethylcarbamate.

1 82-methyl-5 ,7-dichlor-1,2,3 ,4-tetrahydro-N- methylcarbamate.

EXAMPLE 1 l parts of active agent according to the invention and 5 partsof talcum were mixed and finely ground. By mixing in a further 90 partsof talcum, a 5 percent dusting powder was obtained as a starting mixturefor a dilution row of active agent for testing against stored productpests or filter paper in glass dishes. 2 gm of this mixture per glassdish corresponds to 100 mg active substance/m By further l:1 dilutionsof the 5 percent dusting powder, 2.5, 1.25, 0.62, 0.31, 0.16 and 0.08percent mixtures were obtained, which correspond to active substanceconcentrations of 50, 25, 12.5, 6.2, 3.1 and 1.5 mg active substance/m,if 2 g of the particular dust is used per glass dish.

Evaluation after 24 hours showed that the following minimumconcentrations (mg active substance) were necessary for total kill ofthe corresponding pests.

action) or only from above in the direction of the shoot axis(penetration action). In the latter case, test ani-' mals sitting on theunderside of the leaves were not subjected to the spray stream. 11 aftertwo days 100 percent kill was obtained, then the plants were reinfested.

Results were as follows:

a. The test with Epilachna vurivestis, the Mexican bean weevil wascarried out as follows: 4-5 seedlings of lhasenlus vulgaris in the firstleal' stage, in a flowerpot, were dipped in an emulsion of the testpreparation and then allowed to dry. The test animals, L-4 stage of theweevils, were introduced into a cellophane bag which was then fixed overthe treated plants with a rubber band. After 5 days the effect of thetreatment was assessed by counting living and dead animals and count-Active Blatella Periplaneta Blatta ing the percentage kill. substancegermanica amerieana orientalis No. adults L-S L-5 l 1.5 3 4 2 6 3 3Concen- Active 2 g, 1% 4O tration substance 8 l2 2 (ppm) No. 1. 2 6 2230 46 17 12 800 100 100 100 100 10 18 12 0 100 9 12 6 400 100 100 100100 100 100 23 l2 200 100 100 100 100 100 100 16 12 100 100 100 80 60 8080 Active Tenebrio Dermestes Acheta .Sitophilus substance molitorfrischii domestieus granarius No. image Larven Imago Larven L. 1m.

1 50 l2 3 2 50 l2 6 6 6 5 l2 12 6 EXAMPLE 12 Action against Aphis fabaeYoung Vicia faba plants of about 5 cm high were infected with plantparts from plants attached by Aphis fabae. After five days furthergrowth of the plants and a corresponding increase in the number ofaphids, the starting conditions for the active agent test were set up.The infested plants were sprayed from all sides with an emulsion of theactive substances to be tested (contact b. The test with Orgyagonostigma in the L-3 stage was analogously carried out with youngmallow plants (Malva silvestris) as host plants. 5 larvae were used foreach test. Evaluation took place after 2 and 5 days. if total mortalitywas present after 2 days, then the plants were reinfected. In this wayany aging of the layer of active substance during the evaluation couldbe observed.

Results are shown in the following table.

Comp. No. Conc. (ppm) After 2 days After 5 days EXAMPLE 14 Actionagainst beet bugs (Rhodnius prolixus). Acetonic solutions of activesubstance were so applied to petri dishes of 11 cm diameter thatconcentrates of 1 mg, 0.1 mg, 0.01 mg and 0.001 mg per dish wereguaranteed. (1 mg per dish corresponds to 1 g per 9.4 m 20 bugs in theL3 stage were put on the active substance layer for 24 hours, theprepared dishes having been dried for 1 hour. Action was tested after 24hours.

Least concentration (mg/dish) Compound No.

EXAMPLE 15 Action against Aedes aegypti Female mosquitoes (Aedesaegypti) were set on a layer of the test substance in petri dishes of l1 cm diameter for 6 hours. To make the layer 1 ml of an acetonicsolution of the active substance was used and dried for 1 hour.Concentrations of 1000, 100, 10 and 1 ppm were used. These toapplication rates of 1, 0.1, 0.01 and 0.001 mg/dish.

Each 10 ice-cooled mosquito females were counted into the dishes. 4repeats per concentration were conducted.

Active substances 1, 2, 4, 5, 7, 8, 10, 17, 19,22, 23, 27, 28, 29, 30,31, 42 and 46 show 100 percent kill at a concentration of 0.001 mg/dish.

EXAMPLE 16 A. Rhipicephalus bursa Five adult ticks or 50 tick larvaewere counted into a glass test tube and dipped for 1 to 2 minutes in 2ml of an aqueous emulsion from a dilution row of 100, 10, 1 and 0.1 ppmtest substance. The test tube was then closed by a standard cotton-woolplug and placed on its head, so that the emulsion of active substancewas taken up by the cotton wool.

Evaluation took place for adults after 2 weeks and for larvae after 2days. Each test was repeated twice. percent kill was found at thefollowing boundary con centrations.

Active substance No. Rhipicephalus bursa Adults Larvae 4 10 10 10 S l l9l0 5 28 10 0.1 29 10 l B. Boophilus microplus (Larvae) With a similardilution row as in test A, tests were carried out with 20 sensitive and20 OP-resistant larvae (resistance concerned tolerance of diazinone).100 percent kill was observed at the following boundary Action againstspider mites Dwarf bean plants (Phaseolus vufgaris) in the two leafstage were infected 12 hours before the application of active substancewith spider mites by laying on attacked leaf pieces from a culture, sothat after expiration of that time, a population was present on theplants in all stages of development. With the aid of a chromatographyatomiser, the plants were then sprayed with the emulsified activesubstance until an even layer of droplets was present on the leafsurface. Evaluation took place after 2 and 7 days: the plant parts wereinspected under a stereo microscope for reckoning the percentage kill,

In the following table, the percentage kill of the normally sensitivetype Tetranychus urticae Koch are give- 21 22 in which R is hydrogen ormethyl; R is methyl or ace- 8. The compound tyl; R is hydrogen, methyl,allyl, 2-propynyl or methyl 7 cyanato; R is methyl or ethyl; and R ishydrogen, methyl or chlorine. i\J

2. The compound Czlzlg o J O- -NHCHQ CH3 g CH: I 10 9. The compound femV H 3. The compound I I O N CH3 V V it CH:

CH3NH-C-O CH,CH=CH,

II I l CH3 CH: V 10. The compound 4. The compound 7 V '7 V C H K MW 7 s,V A K N H H3C HN omc N u cH, O J

s t W 111 The compound 5. The compound "E l'fifl m CZHE H CHNG-O CH II ICH ll CH3 0 N 3 0 N\/ 0 CH3 H;

6. The compound The Compound W H3O T v 7 7 Wm 40 "TITITT'-H;CVHT\TNC;OVV(1 5265 o N CH3 /N-?O H V H30 3 /N CH3 JOEE;

V 7 13. The compound 7. The compound 7 v v 7' I oi rT 7 V A NC-0 CH CENW HaCHN-|C-O H on, I l Cm N cm OH;

I CH3 I H3 UNITED STATES PATENT @FFICE QERTEFEQATE 9F CGRREfiTWN PatentN 3', 8181012 Dated June 18, 1974 Izkventor(s) Erwin Nikles It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 20, claim 1, line 63, in the formula, delete "R and substitute RSigned and seaied this 18th day of February 1975.

(SEAL) Attest:

C. MARSHALL DANN RUTH Ca MASON Commissioner of Patents Attesting Officerand Trademarks 'ORM PO-105O (10-69) USCOMM-DC 6037 6-P59 us. GOVERNMENTPRINTING OFFICE: I969 o-sse-a34.

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